CN108793120A - The preparation of the double MOF base porous carbon materials of hydrophobicity - Google Patents
The preparation of the double MOF base porous carbon materials of hydrophobicity Download PDFInfo
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- CN108793120A CN108793120A CN201810773309.2A CN201810773309A CN108793120A CN 108793120 A CN108793120 A CN 108793120A CN 201810773309 A CN201810773309 A CN 201810773309A CN 108793120 A CN108793120 A CN 108793120A
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- mof
- porous carbon
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a kind of preparations of the double MOF base porous carbon materials of hydrophobicity, and the method comprises the following steps：According to a certain percentage after mixing by MOF-5 materials and another kind iron-based MOF materials, by its high temperature cabonization, obtain hydrophobicity porous carbon materials, the method of the invention preparation process is simple, product has larger specific surface area and abundant duct, while by iron catalytic graphite method, improving the degree of graphitization of porous carbon materials, to improve its hydrophobicity, there is preferable application prospect in terms of adsorbing separation.
Description
Technical field
The invention belongs to the preparation fields of porous carbon materials, and in particular to a kind of double MOF base porous carbon materials of hydrophobicity
It prepares.
Background technology
Metal-organic framework materials (Metal Organic Frameworks, abbreviation MOFs) are by organic ligand and metal
Ion is keyed the class zeolitic material with periodic network structure being self-assembly of with coordinate covalence.With traditional sorbing material
It compares, this kind of new material has porosity height, specific surface area huge (up to 7000m2/ g), pore structure design is controllable, surface can
The features such as modified, makes it have huge application prospect and development potentiality in terms of the storage of gas, adsorbing separation and catalysis.
However, since MOFs is the dimensional network structure crystal formed by coordinate bond and inorganic metal center hydridization, with other
Porous material is compared, and the stability of MOFs materials is relatively poor.Such as MOF-5 (also referred to as IRMOF-1) is having item existing for steam
Under part, the BET of MOF-5 can be by original 900m2/ g, drops to 45m2/ g, skeleton structure are caved in completely.So its industry is answered
With being greatly limited, the practical application of material is made to be encountered by great challenge.In order to be pushed further into MOFs materials
Application process is heated labile disadvantage using MOFs materials, its high-temperature calcination is carbonized and prepares stable porous carbon materials.
For porous carbon materials because itself having many excellent characteristics, such as easily modification, stable physicochemical properties, heat are steady
Qualitative high and stable mechanical performance etc. and extensively and profoundly studied by scientists.Currently, the preparation method master of porous carbon materials
There are soft template method and hard template method.The porous carbon that soft template method is prepared have can modulation microstructure and form, but
They must accurately design, suitable carbon source and carbonisation is selected to complete the preceding organic formwork thermally decomposed, therefore at present
The soft template that can be used is seldom.Hard template method can prepare the orderly of similar hard template (zeolite molecular sieve, mesoporous silicon etc.)
The porous carbon of pore structure, but usually its preparation process is complex, is not suitable for industrialized production and application.Therefore, more in order to be promoted
The performance of hole carbon material expands its application range, and there is an urgent need to improve and perfects for the preparation method of porous carbon.Using MOFs as raw material
The process for preparing porous carbon is simple and practicable, and does not need template, this just provides new finger for the preparation of porous carbon materials and application
Draw.MOFs bases porous carbon materials are by (aperture is controllable, surface chemical property is adjustable etc.) the advantages of MOFs and porous carbon materials itself
Excellent specific property (flourishing gap structure, outstanding chemically and thermally stability etc.) be combined together so that it is final prepared
Porous carbon materials show excellent performance in gas absorption application.But the relative humidity of the long-term air of southern region of China is all
In 60~90% ranges, being greatly lowered for its gas absorption capacity is led to due to the significantly strong competitive Adsorption of hydrone.Cause
The novel MOF bases porous carbon materials of this research hydrophobicity are imperative.And the degree of graphitization for increasing porous carbon means that and subtracts
The content for having lacked surface hydrophilic group improves its surface hydrophobic, to greatly weaken competition of the hydrone to gas molecule
Absorption.It is reported that graphited porous carbon materials can be prepared using transition metal (Fe, Co, Ni etc.) catalyzed graphitization method.Such as
(Zhang et al., the Structural Evolution from Metal-Organic Framework to such as Zhang
Hybrids of Nitrogen-Doped Porous Carbon and Carbon Nanotubes for Enhanced
Oxygen Reduction Activity.Chemistry of Materials, 2015,27,7610-7618) report with
MOF-5 and urea use Ni as graphitization catalyst, are successfully prepared nitrogenous graphite porous carbon/carbon and receive as carbon source and nitrogen source
Mitron composite material.But this method step is complicated, needs after first MOF-5 is tentatively carbonized, is re-introduced into W metal salt, high again
Warm carbonized graphite.Therefore, it is necessary to seek a kind of new method preparing hydrophobicity MOF base porous carbon materials.
Invention content
The purpose of the present invention is to provide a kind of preparation of the double MOF base porous carbon materials of hydrophobicity, prepared by this method
Porous carbon has high-specific surface area and relatively rich grade pore structure, and has good hydrophobicity.
In order to realize that above-mentioned technical purpose, the technical solution adopted by the present invention be：
A kind of preparation method of the double MOF base porous carbon materials of hydrophobicity comprising following steps：
(1) MOF-5 materials are uniformly mixed with iron-based MOF materials by different quality ratio, mixture is made；
(2) after mixture made from step (1) being carried out high temperature cabonization processing, the double MOF base porous carbons of hydrophobicity are made
Material.
Further, the iron-based MOF materials described in step (1) are MIL-100 (Fe) or MIL-101 (Fe).
Further, the mixing quality ratio of MOF-5 materials and iron-based MOF materials is 2~6: 1 in step (1).
Further, step (1) is mixed into physical mixed.
Further, the processing of high temperature cabonization described in step (2) is that mixture is warming up to 600~900 under nitrogen protection
DEG C, and 5~8h is maintained at such a temperature.
Preferably, 600~900 DEG C are warming up to the heating rate of 2~10 DEG C/min in step (2).
It is according to the application of the double MOF base porous carbon materials of hydrophobicity made from above-mentioned preparation method, hydrophobicity obtained is double
Adsorbing separation of the MOF base porous carbon materials for gas purifies.
The principle of the present invention is：
The method of the present invention for preparing the double MOF base porous carbon materials of hydrophobicity is to use double MOF for template and carbon source,
Middle MOF-5 has abundant micropore, and another kind iron-based MOF materials (MIL-100 (Fe), MIL-101 (Fe)) are with abundant
Middle micro-diplopore structure, to have the porous carbon materials in abundant duct conducive to formation.In addition, MIL-100 (Fe) and MIL-101
(Fe) contain iron, can be during high temperature cabonization, catalyzed graphitization, to improve the hydrophobicity of porous carbon materials.
Using above-mentioned technical solution, the device have the advantages that being：
(1) present invention uses double MOF materials for template and carbon source, and it is double to be prepared for hydrophobicity by simple one step carbonization
MOF base porous carbon materials；
(2) double MOF bases porous carbon materials prepared by the present invention, while there is abundant micropore and central hole structure, micropore pair
Adsorbate has strong adsorption, is conducive to the absorption of adsorbate, and mesoporous is conducive to the diffusion of adsorbate；
(3) using double MOF bases porous carbon materials prepared by the method for the invention has good hydrophobicity, double MOF bases
Porous carbon materials are far below original MOF-5 materials to the adsorption capacity of water vapour.
Description of the drawings
The present invention is further elaborated with reference to the accompanying drawings and detailed description：
The double MOF base porous carbon materials of hydrophobicity that Fig. 1 is MOF-5 prepared by the embodiment of the present invention 1 and prepared by embodiment 2
N2Adsorption/desorption isotherms；
The double MOF base porous carbon materials of hydrophobicity that Fig. 2 is MOF-5 prepared by the embodiment of the present invention 1 and prepared by embodiment 2
XRD spectra；
The double MOF base porous carbon materials pair of hydrophobicity that Fig. 3 is MOF-5 prepared by the embodiment of the present invention 1 and prepared by embodiment 2
The adsorption isotherm of water vapour.
Specific implementation mode
Embodiment 1
For ease of the effect of the synthetic method of the double MOF base porous carbon materials of comparative illustration hydrophobicity of the present invention, implement
Example 1 provides a kind of MOF-5 materials prepared according to conventional method, and specific preparation method is as follows：
By 9.88g Zn (OAC)2·2H2O and 2.49g terephthalic acid (TPA)s (H2BDC 350mL dimethylformamides) are dissolved in
(DMF) in, 5h is stirred at room temperature and obtains reaction product；Reaction product is centrifuged, ethyl alcohol is washed, the dry 8h of 150 DEG C of vacuum to get to
MOF-5 materials.
Embodiment 2
A kind of preparation method of the double MOF base porous carbon materials of hydrophobicity, includes the following steps：
0.6g MOF-5 materials and 0.1g MIL-100 (Fe) are put into tube furnace after mixing, under nitrogen protection with
5 DEG C/min is warming up to 900 DEG C and maintains 6h to get to the double MOF base porous carbon materials of hydrophobicity.
Embodiment 3
A kind of preparation method of the double MOF base porous carbon materials of hydrophobicity, includes the following steps：
0.56g MOF-5 materials and 0.14g MIL-100 (Fe) are put into tube furnace after mixing, under nitrogen protection
Being warming up to 900 DEG C with 10 DEG C/min maintains 5h to get to the double MOF base porous carbon materials of hydrophobicity.
Embodiment 4
A kind of preparation method of the double MOF base porous carbon materials of hydrophobicity, includes the following steps：
0.58g MOF-5 materials and 0.12g MIL-101 (Fe) are put into tube furnace after mixing, under nitrogen protection
Being warming up to 800 DEG C with 5 DEG C/min maintains 7h to get to the double MOF base porous carbon materials of hydrophobicity.
Embodiment 5
A kind of preparation method of the double MOF base porous carbon materials of hydrophobicity, includes the following steps：
0.6g MOF-5 materials and 0.1g MIL-101 (Fe) are put into tube furnace after mixing, under nitrogen protection with
2 DEG C/min is warming up to 700 DEG C and maintains 6h to get to the double MOF base porous carbon materials of hydrophobicity.
Embodiment 6
A kind of preparation method of the double MOF base porous carbon materials of hydrophobicity, includes the following steps：
0.5g MOF-5 materials and 0.1g MIL-100 (Fe) are put into tube furnace after mixing, under nitrogen protection with
5 DEG C/min is warming up to 600 DEG C and maintains 8h to get to the double MOF base porous carbon materials of hydrophobicity.
Performance detection is analyzed
As a control group with MOF-5 materials made from embodiment 1, then with embodiment 2 the double Quito the MOF holes of hydrophobicity prepared
The characterization result of carbon material is the effect that representative illustrates the present invention, the double MOF base porous carbons of hydrophobicity prepared by other embodiments
The characterization result of material is not just provided and is repeated one by one substantially with embodiment 2.
(1) specific surface area and pore structure property representation of MOF-5 and double MOF base porous carbon materials：
Adsorption instrument 3Flex is mostly used to embodiment 1 using three station full functions of Micromertics companies of U.S. production
The specific surface area and pore structure of MOF-5 materials and double MOF bases porous carbon materials of embodiment 2 are characterized, as a result such as table 1
It is shown.
The specific surface area and parameter of pore structure of 1 MOF-5 of table and double MOF base porous carbon materials
By table 1 it can be seen that the BET specific surface area of original MOF-5 is 1030.1m2·g-1.And use side of the present invention
Double MOF bases porous carbon materials specific surface areas prepared by method are 1552.6m2·g-1, total pore volume is up to 2.04cm3·g-1, micropore hole
Hold up to 0.51cm3·g-1, mesopore volume is up to 1.53cm3·g-1, illustrate double MOF bases porous carbon materials that embodiment 2 obtains
With large specific surface area and higher porosity, and there is middle micro-diplopore skeleton structure.
Fig. 1 is the N of MOF-5 prepared by Examples 1 and 2 and double MOF base porous carbon materials2Adsorption/desorption isotherms.By Fig. 1
It is found that the adsorption isotherm of double MOF bases porous carbon materials prepared by embodiment 2 is different from MOF-5, double MOF prepared by embodiment 1
Base porous carbon materials are to N2Adsorbance gradually risen with the increase of pressure, and there is hysteresis loop, it is rich to show that the material has
Rich central hole structure.
(2) crystal structure properties of double MOF bases porous carbon materials：
Double MOF that the D8-ADVANCE models X-ray diffractometer produced using German Bruker companies prepares embodiment 2
The crystal structure of base porous carbon materials is characterized.The results are shown in Figure 2.
Figure it is seen that double MOF bases porous carbon materials prepared by the embodiment of the present invention 2 occur at 2 θ=44.8 °
The characteristic diffraction peak of Fe.In addition there is a peak at 43.8 ° near the peak, be attributed to the characteristic peak of graphitic carbon, show double
MOF bases porous carbon materials are provided with certain degree of graphitization under the catalytic action of Fe.
(3) MOF-5 and double MOF bases porous carbon materials are to the absorption property of water vapour：
Adsorption instrument 3Flex is mostly used using three station full functions of Micromertics companies of U.S. production to measure under 298K in fact
The MOF-5 materials of example 1 and double MOF bases porous carbon materials of embodiment 2 are applied to the adsorption isotherm of water vapour.Before sample test
Pretreatment condition be：By sample vacuum drying 8h at 150 DEG C, vacuum degree is 5~10Pa.The results are shown in Figure 3.
By Fig. 3, it can be seen that, the capillary pressure curve of double MOF bases porous carbon materials of embodiment 2 is significantly lower than MOF-5
Material.In 298K and 1.2kPa, double MOF bases porous carbons of embodiment 2 are 1.3mmolg to the adsorbance of water vapour-1, and
MOF-5 is up to 4.4mmolg to the adsorbance of water vapour-1.This shows double MOF that hydrophobicity is prepared for using the method for the present invention
Base porous carbon materials.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of the double MOF base porous carbon materials of hydrophobicity, it is characterised in that：It includes the following steps：
（1）MOF-5 materials are uniformly mixed with iron-based MOF materials by different quality ratio, mixture is made；
（2）By step（1）After mixture obtained carries out high temperature cabonization processing, the double MOF base porous carbon materials of hydrophobicity are made.
2. a kind of preparation method of the double MOF base porous carbon materials of hydrophobicity according to claim 1, it is characterised in that：Step
Suddenly（1）Described in iron-based MOF materials be MIL-100 (Fe) or MIL-101 (Fe).
3. a kind of preparation method of the double MOF base porous carbon materials of hydrophobicity according to claim 1, it is characterised in that：Step
Suddenly（1）The mixing quality ratio of middle MOF-5 materials and iron-based MOF materials is 2~6: 1.
4. a kind of preparation method of the double MOF base porous carbon materials of hydrophobicity according to claim 1, it is characterised in that：Step
Suddenly（1）Be mixed into physical mixed.
5. a kind of preparation method of the double MOF base porous carbon materials of hydrophobicity according to claim 1, it is characterised in that：Step
Suddenly（2）Described in high temperature cabonization processing for mixture is warming up to 600~900 DEG C under nitrogen protection, and tie up at such a temperature
Hold 5~8 h.
6. a kind of preparation method of the double MOF base porous carbon materials of hydrophobicity according to claim 5, it is characterised in that：Step
Suddenly（2）In with the heating rate of 2~10 DEG C/min be warming up to 600~900 DEG C.
7. according to the application of the double MOF base porous carbon materials of hydrophobicity made from one of claim 1 to 6 preparation method,
It is characterized in that：Adsorbing separation by the double MOF base porous carbon materials of hydrophobicity obtained for gas purifies.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112619608A (en) * | 2021-01-11 | 2021-04-09 | 福州大学 | Preparation and application of glucose-based porous carbon material |
| CN113289579A (en) * | 2021-05-26 | 2021-08-24 | 吉林化工学院 | Metal organic framework derived magnetic porous carbon material and extraction of 4 organic dyes in beverage by using same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229768A (en) * | 2014-07-01 | 2014-12-24 | 江西师范大学 | Method for preparing porous carbon with three-dimensional structure |
| CN104418315A (en) * | 2013-08-22 | 2015-03-18 | 苏州奥索特新材料有限公司 | Preparation method of ordered mesoporous carbon material with high specific surface area by using metal organic skeleton |
| CN105217600A (en) * | 2015-10-23 | 2016-01-06 | 深圳大学 | A kind of take MOFs as the method for Template preparation porous carbon materials |
| CN106563415A (en) * | 2016-11-04 | 2017-04-19 | 南昌大学 | Method for preparing MIL-100Al-based porous carbon material for carbon dioxide adsorption and separation |
| WO2017192728A1 (en) * | 2016-05-03 | 2017-11-09 | Virginia Commonwealth University | Heteroatom -doped porous carbons for clean energy applications and methods for their synthesis |
| CN107399729A (en) * | 2017-06-28 | 2017-11-28 | 中山大学 | A kind of bimetallic MOFs nitrogenous graphitized carbon material |
-
2018
- 2018-07-14 CN CN201810773309.2A patent/CN108793120B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104418315A (en) * | 2013-08-22 | 2015-03-18 | 苏州奥索特新材料有限公司 | Preparation method of ordered mesoporous carbon material with high specific surface area by using metal organic skeleton |
| CN104229768A (en) * | 2014-07-01 | 2014-12-24 | 江西师范大学 | Method for preparing porous carbon with three-dimensional structure |
| CN105217600A (en) * | 2015-10-23 | 2016-01-06 | 深圳大学 | A kind of take MOFs as the method for Template preparation porous carbon materials |
| WO2017192728A1 (en) * | 2016-05-03 | 2017-11-09 | Virginia Commonwealth University | Heteroatom -doped porous carbons for clean energy applications and methods for their synthesis |
| CN106563415A (en) * | 2016-11-04 | 2017-04-19 | 南昌大学 | Method for preparing MIL-100Al-based porous carbon material for carbon dioxide adsorption and separation |
| CN107399729A (en) * | 2017-06-28 | 2017-11-28 | 中山大学 | A kind of bimetallic MOFs nitrogenous graphitized carbon material |
Non-Patent Citations (1)
| Title |
|---|
| 陈泽华等: "《钒电池的应用与研究》", 30 November 2016, 吉林大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112619608A (en) * | 2021-01-11 | 2021-04-09 | 福州大学 | Preparation and application of glucose-based porous carbon material |
| CN112619608B (en) * | 2021-01-11 | 2022-04-01 | 福州大学 | Preparation and application of glucose-based porous carbon material |
| CN113289579A (en) * | 2021-05-26 | 2021-08-24 | 吉林化工学院 | Metal organic framework derived magnetic porous carbon material and extraction of 4 organic dyes in beverage by using same |
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